The power of trichlorosilylation: isolable trisilylated allyl anions, allyl radicals, and allenyl anions.

Treatment of hexachloropropene (ClC[double bond, length as m-dash]C(Cl)-CCl) with SiCl and [BuN]Cl (1 : 4 : 1) in CHCl results in a quantitative conversion to the trisilylated, dichlorinated allyl anion salt [BuN][ClC[double bond, length as m-dash]C(SiCl)-C(SiCl)] ([BuN][]). Tetrachloroallene ClC[double bond, length as m-dash]C[double bond, length as m-dash]CCl was identified as the first intermediate of the reaction cascade. In the solid state, [] adopts approximate symmetry with a dihedral angle between the planes running through the olefinic and carbanionic fragments of [] of C[double bond, length as m-dash]C-Si//Si-C-Si = 78.

One tool to bring them all: Au-catalyzed synthesis of B,O- and B,N-doped PAHs from boronic and borinic acids.

The isoelectronic replacement of C[double bond, length as m-dash]C bonds with B[double bond, length as m-dash]N bonds in polycyclic aromatic hydrocarbons (PAHs) is a widely used tool to prepare novel optoelectronic materials. Far less well explored are corresponding B,O-doped PAHs, although they have a similarly high application potential. We herein report on the modular synthesis of B,N- and B,O-doped PAHs through the [Au(PPh)NTf]-catalyzed 6--dig cyclization of BN-H and BO-H bonds across suitably positioned C[triple bond, length as m-dash]C bonds in the key step.